Microsphere-Based Coatings for Radioactive Cooling Under Direct Sunlight

ABSTRACT

The present prevention provides a surface coating for cooling a surface by light scattering comprising a plurality of successive layers, each of the layers may be comprised of a plurality of spheres arranged to form a structure comprised of packed spheres. Each layer may have a different arrangement of packed spheres to create to a different light scattering property in each of the layers. The coating of the structures may also be formed by randomly packed spheres and the spheres may have a uniform diameter.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/242,483, filed Oct. 16, 2015 and herein incorporated by reference.This application also claims the benefit of U.S. Provisional ApplicationNo. 62/293,225, filed Feb. 9, 2016 and herein incorporated by reference.

BACKGROUND OF THE INVENTION

In the field of photonic crystals—artificial materials that possess aperiodicity on the order of an optical length scale, the structuraldisorder is a problem in many cases as it scatters light randomly. Whiledefects can be intentionally introduced in photonic crystals for lightlocalization, random scattering of light in photonic crystals is ingeneral a consequence of fabrication errors. However, curiously, manyphotonic patterns found in animals and plants are not perfectlyperiodic. For example, butterfly wings, humming birds, or blue Polliafruits generate iridescent colors by employing periodic structures butthe structures involve a degree of disorder that is much greater thanthat in typical photonic crystals fabricated by current nanopatterningtechniques. If the structures in nature have been optimized, asgenerally thought, over hundreds of million years of evolution forvarious purposes such as signaling, mating, camouflage, and seeddispersing, it may suggest that a certain degree of structuralrandomness is actually not only favorable but even required for the bestoptical performance in many applications.

When structural randomness is present, light propagation can be dividedinto two modes: direct propagation and random scattering. The randomscattering resembles diffusive transport of particles in many respects.In the diffusion picture of light propagation, energy packets areconsidered to perform a random walk due to the irregular structures. Animportant parameter in this picture is the transport mean free path, l*,which is defined as the average distance that an energy packet travelsbefore its propagation direction has no correlation with its originaldirection. The transport mean free path is to be distinguished from thescattering mean free path, l, which is the average distance over whichlight propagates without scattering. Therefore, l* is larger than l andthey are closer to each other as the scattering of a constituentparticle is stronger. While the diffusion picture considers thetransport of energy packets only, the wave nature of light such asinterference is still preserved in random media. For example, backscattered light interferes always constructively and multiply scatteredlight can be localized in strongly scattering media due to interference,a phenomenon known as Anderson localization. In the embodiments of thepresent invention, the scattering, in most instances, will not be verystrong, so that kl>>1, where k=2πn/λ with λ the wavelength of light infree space and n the average refractive index of the random media.Therefore, the light transport in the proposed work is well described bythe diffusion picture.

Materials can cool under direct sunlight even below an ambienttemperature. The cooling effect is achieved by minimizing solarabsorption and maximizing heat radiation into an atmospheric windowwhich is mostly within 8-13 μm in light wavelength. Prior art in apatent US 2014/0131023 achieved the cooling effect using multilayerstructures. However, in these structures, the thickness of each layerneeds to be precisely controlled within a few nanometers to efficientlyblock sunlight absorption. The sunblock performance of these structuresdegrades when applied to surfaces of high curvatures. Moreover, forpractical applications, the fabrication of many layers over a large areapresents manufacturing challenges in terms of throughput and cost. Incomparison, paint-based coatings are much more convenient andcost-effective. Paints can be applied on highly curved surfaces withoutloss in cooling performance Further, no precision control is required inapplying paints on surfaces.

Solar heat preventive paints are typically based on particles of silica,borosilicate, titania, etc. While pigments that are non-white and highlyreflective in near-infrared (IR) are used to reduce solar heating, thesepigments are absorptive in the visible spectrum and hence less effectivein cooling. For white paints, when the pigments are made of lowrefractive index materials such as silica, the particles are of a hollowspherical shell shape to enhance sunlight scattering. As in a U.S. Pat.No. 7,503,971, these particles are typically large compared to solarspectral wavelengths and ranges from 20 to 150 μm in size. As theparticle size is large, the sunlight scattering efficiency is low andthick coatings are required to efficiently block sunlight. For highrefractive index particles such as titania, current paint technology hasdetermined that the particle size should be close to 200-250 nm tomaximize whiteness of coatings.^(1, 2) While this size maximizes thescattering of visible wavelengths, these coatings suffer from solarheating due to weak scattering of near IR. Even commercial solarIR-blocking paints use particles of 200-250 nm in size.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the present invention provides a significantdeparture from the conventional approaches, where the entire microspherepacking assumes a specifically ordered photonic lattice structure or acompletely random photonic glass structure.

In yet other embodiments, the present invention provides optimumparticle sizes and volume fractions to maximize the cooling effect ofpaints under direct sunlight.

In one embodiment, the present invention provides designs andfabrication methods to create tiered structures. Each tier may be amonolayer or multilayer of microspheres with a prescribed degree ofrandomness. Each tier may also assume a well-defined structure with alateral periodicity. The random and well-defined structures may alsoalternate from tier to tier.

In one embodiment, the present invention uses structural manipulationand an understanding of light scattering in the microsphere media totailor light absorption in the materials that sit underneath thescattering media in a prescribed fashion. For instance, suchmanipulation allows efficient control of light scattering to realizecoatings that (1) prevent or (2) optimally allow sunlight absorption inthe underlying materials.

In other embodiments, the coatings may simultaneously and efficientlyremove heat by thermal radiation, so that the underlying materials cooleven under the direct sunlight. In a preferred embodiment, when thecoatings when the coatings of the present invention provide strong lightscattering to prevent sunlight absorption, the temperature of theunderlying material may be 30 to 40° C. below the ambient temperatureeven under the direct sunlight. Such passive cooling effect would betremendously beneficial to energy savings for summer time with zerooperating cost. In another preferred embodiment of the presentinvention, for optimal sunlight absorption, the coatings efficientlytrap sunlight in the underlying material, while radiatively removingheat from the underlying material. This efficient light trapping andcooling would be particularly beneficial in achieving high efficiency insolar cells.

In yet other embodiments, the present invention providesmicrosphere-based coatings that are inexpensive and amenable to highthroughput processing for manufacturability with applications in energyharvesting, building construction, transportation, space vehicles, andelectronic displays.

In other embodiments, the present invention enables controlled lightscattering including extremely strong and weak scattering.

In other embodiments, the present invention provides materialtemperatures that are 30-40° C. below the ambient temperature underdirect sunlight will be realized by passive radiative cooling usinginexpensive microsphere-based coatings.

In other embodiments, the present invention provides both light trappingand radiative cooling at the same time in solar cells usingmicrosphere-based coatings.

In another embodiment, the present prevention provides a surface coatingfor cooling a surface by light scattering comprising a plurality ofsuccessive layers, each of the layers comprised of a plurality ofspheres arranged to form a structure comprised of packed spheres ornon-packed spheres and each structure of each layer has a differentarrangement of packed spheres or non-packed spheres to create to adifferent light scattering property in each of the layers. The coatingof the structures may also be formed by randomly packed spheres and thespheres may have a uniform diameter. In yet other embodiments, thecoating reflects and emits light in a range of 8-13 microns. In yetanother embodiment, the coating reflects and/or emits light in a rangeof 18-30 microns.

In yet another embodiment, the coatings of the present invention havespheres that are comprised of hollow spheres having a shell that traps agas inside the sphere, the shell has refractive index that is differentthan the gas. The spheres may range in size from 1-3 microns and theshells may have a thickness that ranges in size from 1-10 nm.

In still further embodiments, the coating has layers which may have afixed periodicity and the periodicity of each layer is different. Thelayers may alternate between periodic and non-periodic structures.

In yet other embodiments, the coatings have structures which may be madeof multilayers of spheres with a predetermined degree of randomness. Insome embodiments, the periodic layers are ordered structures and thenon-periodic structures are random structures. In further embodiments,the layers are made of a monolayer of microspheres with a predetermineddegree of randomness.

In a preferred embodiment, the coatings of the present invention areconstructed of layers in the layers have a sphere filling fraction ofless than 55% or between 20-45% and said spheres have a diameter between0.4 and 1 micron. In other aspects, the layers have a sphere fillingfraction of less than 30% and the spheres have a diameter of 1 micron orless.

In yet other embodiments, the coatings of the present invention may becomprised of layers which have spheres joined into fibrillar networksand the fibrillar networks of each layer have different periodicitiesand orientations.

In yet other embodiments, the present invention provides methods forcooling a substrate by applying a coating to the surface of thesubstrate comprising the steps of applying layers of spheres wherein thecooling power is enhanced by decreasing the sphere filling fraction to afilling fraction of less than 55% in each of the layers. In otheraspects, the filling fraction is less than 30% and the spheres have auniform diameter of 1 micron or less.

In yet other embodiments, the method of the present invention includescreating monolayers of hexagonally arranged spheres which aretransferred onto the substrate. In other aspects, the transferring stepis repeated to form multiple layers on the substrate. In yet otheraspects, the transferring step is repeated to form multiple layers onthe substrate with each layer having a differing arrangement of spheresby varying the surface pressure used to make each layer, by varying thesubstrate pulling speed used to make each layer, or both.

In other embodiments, the layers may be comprised of tiers of randomlydistributed spheres and the degree of randomness of each tier with eachsuccessive layer added to the substrate increases or varies. The layersmay be made using the sedimentation of colloidal spheres to createrandom layers of microspheres. The spheres and substrate may also beadapted to have attractive charges to create random layers ofmicrospheres.

In addition, in other embodiments the random layers are made by inducingcolloidal instability.

In yet other embodiments, the layers are made using spray coating forthe fabrication of randomly packed spheres and the spheres and thesubstrate are adapted to have attractive charges to cause the spheresbind together and to the substrate to have a random sphere packingdensity that is lower than 55%. In other aspects, the coating is appliedat a temperature of ˜130° C.

In yet other embodiments, the method of the present invention includesapplying a coating to the surface of a substrate comprising the steps ofapplying spheres arranged in fibrillar networks to form successivelayers of spheres and wherein at least one of the fibrillar networks mayinclude at least one kinked chain of microspheres.

In yet other embodiments, the method of the present invention includesapplying a coating to the surface of a substrate comprising the steps ofapplying polyethylene by fiber spinning to create layers of fibrillarnetworks.

In yet other embodiments, the method of the present invention includesapplying a coating to the surface of a substrate by depositingpolyethylene to the substrate surface. In other aspects, thepolyethylene is co-deposited with one or more other materials that aresubsequently etched away.

In yet other embodiments, the method of the present invention includesapplying a coating to the surface of a substrate by forming microbubbleswithin a polyethylene film that is applied to the surface of asubstrate. In other aspects, etching is used to form the microbubbles.

Additional objects and advantages of the invention will be set forth inpart in the description which follows, and in part will be obvious fromthe description, or may be learned by practice of the invention. Theobjects and advantages of the invention will be realized and attained bymeans of the elements and combinations particularly pointed out in theappended claims.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, which are not necessarily drawn to scale, like numeralsmay describe substantially similar components throughout the severalviews. Like numerals having different letter suffixes may representdifferent instances of substantially similar components. The drawingsillustrate generally, by way of example, but not by way of limitation, adetailed description of certain embodiments discussed in the presentdocument.

FIGS. 1A and 1B illustrate diffuse intensity distribution in the twotiers of randomly packed SiO₂ spheres on Si (FIG. 1A) when the first andsecond tiers have l*=3 μm and 30 μm, respectively and (FIG. 1B) when thetwo tiers are interchanged. Light is incident on z=0 plane as shown ininsets.

FIG. 2 illustrates intensity spectra of solar radiation and atmosphericradiation. Each is normalized to its maximum intensity.

FIG. 3 is a Mid-IR emissivity spectrum of solid silica film and silicamicrosphere packing of 55%. The thickness of both films is 100 μm andnormal direction of emission is considered.

FIG. 4 are SEM images and G parameter values (boxed numbers) in micronsfor various combinations of the pulling speed and the surface pressurefor Langmuir-Blodgett (LB) assembled monolayers.

FIGS. 5A and 5B illustrate the optimal pulling speed and the optimalsurface pressure for (FIG. 5A) a monolayer and (FIG. 5B) an additionallayer assembly. The black square dots show the experimental points wherethe G value is the greatest and the lines are model predictions.

FIG. 6A is an SEM image of disordered microspheres.

FIG. 6B shows an autocorrelation function obtained from FIG. 6A.

FIG. 7A illustrates a complete assembly of spray-coating apparatus.

FIG. 7B is a top view of heated stage where the substrate can be placedon the metal platform.

FIG. 7C is a cross-sectional view of the heated, movable stage showingthe linear motor.

FIG. 7D is an SEM image of microsphere coating with 1 stage cycle.

FIG. 7E is an SEM image of microsphere coating with 3 stage cycles.

FIG. 8 illustrates a fabrication process for creating fibrillar networkstructures by microsphere self-assembly.

FIG. 9 is an illustrates an SEM image of microspheres coated on c-Sigrooves by LB technique.

FIG. 10A shows a schematic illustration of order-disorder mixing infibrillar network structures with separate ordered layers (bold circles)and disordered (circles) layers.

FIG. 10B shows intermediate mixing of layers.

FIG. 10C shows random mixing of the original ordered and disorderedlayers.

FIG. 11A illustrates a straight sphere chain depending on the groovewidth.

FIG. 11B illustrates a non-straight sphere chain depending on the groovewidth.

FIG. 12 illustrates calculated solar absorptivity of randomly packedSiO₂ spheres on an absorbing material as a function of the spherecoating thickness at the interface reflectance of 0 and 0.96.

FIG. 13 illustrates cooling power as a function of the temperature ofvarious materials when the ambient temperature is 27° C. The black bodyand the ideal emissivity refer to mid-IR spectrum only. The solarabsorptivity of the materials is 0.034, the same value as the SiO₂coating.

FIGS. 14A and 14B illustrates absorptivity in semi-infinite Si substratewith a perfect antireflection coating due to diffuse light and to bothdiffuse and ballistic light when SiO₂ microspheres are placed on top.(FIG. 14A) l*=3 μm and (FIG. 14B) l*=200 μm.

FIG. 15 is a comparison of experimental results and CPA prediction of l*for randomly packed SiO₂ microspheres of a 0.9 μm diameter. Predictionsare given for two extreme values of filling fraction 0.55 and 0.64 forrandomly packed single size spheres.

FIG. 16 illustrates l* spectra at various sphere diameters d when thefilling fraction is 55%.

FIG. 17 is a CPA prediction of l* as a function of SiO₂ microspherefilling fraction in random packing at selected light wavelengths in thesolar spectrum.

FIG. 18 illustrates dependence of the sunblock power, 1/<l*>, on thediameter and filling fraction of randomly packed SiO₂ microspheres.

FIGS. 19A and 19B are schematic illustrations of sphere polydispersityeffect on filling fraction.

FIG. 20 illustrates dependence of the sunblock power, 1/<l*>, on thediameter and filling fraction of randomly packed TiO₂ microspheres in amedium of refractive index 1.54.

DETAILED DESCRIPTION OF THE INVENTION

Detailed embodiments of the present invention are disclosed herein;however, it is to be understood that the disclosed embodiments aremerely exemplary of the invention, which may be embodied in variousforms. Therefore, specific structural and functional details disclosedherein are not to be interpreted as limiting, but merely as arepresentative basis for teaching one skilled in the art to variouslyemploy the present invention in virtually any appropriately detailedmethod, structure or system. Further, the terms and phrases used hereinare not intended to be limiting, but rather to provide an understandabledescription of the invention.

In one embodiment of the present invention, control of light scatteringis obtained by using tiered structures where each tier has its ownpredetermined characteristic scattering properties. For example, FIG. 1shows diffuse intensity distribution in the two tiers of l*=3 μm and 30μm on Si. In FIG. 1, U_(d) is the diffuse component of the intensityinside the tiers and U₀ is the intensity of incident light. When the twotiers are interchanged, the diffuse intensity distribution isdrastically modified. This permits the fabrication of a plurality oftiers of varying degrees of randomness as well as versatile control ofscattering properties.

The diffusion model gives the steady state diffusion equation for lightpropagation in a slab in the z-direction that is normal to the slabsurface as

$\begin{matrix}{\frac{d^{2}U_{d}}{{dz}^{2}} = {{- \frac{3}{l^{2}}}U_{0}{e^{{- z}/l}.}}} & (1)\end{matrix}$

The ballistic component of the intensity in the media is given by

U_(b)=U₀e^(−1/l).  (2)

When the thickness of the slab, L, is much larger than l*, the solutionto Eq. (1) with appropriate boundary conditions gives transmittance

$\begin{matrix}{{T \cong \frac{1 + z_{e}}{{L/l^{*}} + {2\; z_{e}}}},} & (3)\end{matrix}$

where z_(e) is the extrapolation length normalized by l* and theextrapolation length is the distance outside the slab over which thediffuse intensity vanishes. When the internal reflectance at theboundaries is R, the extrapolation length ratio is given by

$\begin{matrix}{z_{e} = {\frac{2}{3}{\frac{1 + R}{1 - R}.}}} & (4)\end{matrix}$

Equation (3) shows that, roughly, transmittance in a thick slab isinversely proportional to the thickness. With transmittance measurementat various thicknesses, l* and z_(e) can be experimentally determinedusing Eq. (3). The l can be determined from the ballistic transmittanceof, desirably, thin samples. Therefore, the scattering parameters ofeach tier in a multi-tiered stack can be obtained from the measurementon the uniform slabs of the same scattering properties as each tier.

The scattering properties of the multi-tiered stack may be predicted bysolving the diffusion equation with the obtained parameters.Angle-dependent internal reflectance in the equation may also beconsidered because it can account for the change in the diffusetransmission and reflection when the tier distribution in multi-tieredstructures is modified. In solving the diffusion equation, z_(e) wouldbe close to ⅔ for the boundaries between the tiers according to Eq. (4)because the internal reflection at the boundaries would be small.

In other applications, the embodiments of the present invention may beused with solar energy in heating and cooling applications. For example,solar collectors concentrate sunlight in a small area covered with solarselective surfaces. These selective surfaces, that are housed in avacuum, absorb sunlight strongly while minimizing thermal radiation lossin mid-infrared (mid-IR). Compared to heating, the possibility ofcooling by preventing sunlight absorption and maximizing thermalradiation is much less recognized. However, it has been demonstratedthat radiative cooling by a purely passive way can achieve temperatureslying almost 40° C. below the ambient temperature at night. Moreover,studies have shown that, even under direct sunlight, materials can beradiatively cooled to temperatures that are 5° C. below the ambienttemperature. The remarkable radiative cooling performance shows that thepassive cooling technology of the embodiments of the present inventionhave great potential for widespread use in buildings. The inexpensiveradiation cooling technology of the present invention may saveelectrical energy consumption in residential buildings substantiallybecause 87% of U.S. households are equipped with air conditioners. Inaddition to air conditioning in residential buildings, the potentialapplications of radiative cooling of the present invention hasapplication in various interior/exterior automotive parts, outdoornon-residential construction walls, chemical container tanks, electronicdevices with hot spots, and so on.

The cooling power of a material under sunlight is defined by

P _(cool)(T)=P _(rad)(T)−P _(atm)(T _(amb))−P _(sun) −P _(other),  (5)

where P_(rad) is the power radiated by the material, P_(atm) is thepower absorbed by the material from the atmospheric radiation, P_(sun)the power absorbed by the material from the solar radiation, P_(other)is the power transferred to the material from other sources typically byconduction and convection, T is the material temperature, and T_(amb) isthe ambient temperature. T is lowered as the cooling process proceedsand reaches a final value when the cooling power becomes zero. Thecooling power is calculated using the standard solar spectrum such asAM1.5G for P_(sun) and the mid-IR atmospheric radiation spectra forP_(atm). The solar and atmospheric radiation spectra are shown in FIG. 2where each spectrum is normalized by its maximum intensity. These twospectra have little overlap with each other so that each can becontrolled separately. The black body radiation power at 25° C. is ˜450W/m² which is comparable to the solar power that is ˜1000 W/m².Therefore, the control of both solar absorptivity and mid-IR emissivityof a material has substantial effect on the cooling power.

In the mid-IR, P_(rad) and P_(atm) have opposite effects on cooling. Ifatmospheric radiation were a black body spectrum, these two would be thesame at the same temperature. This is because of the Kirchhoff's lawwhich states that absorptivity is the same as emissivity at equilibrium.Thus, if the atmosphere were a black body, the power radiated from thematerial would be the same as the absorbed power by the material.However, the atmospheric radiation spectrum in FIG. 2 exhibits awavelength interval 8≤λ≤13 μm where the radiation is minimal Thus, ifthe material radiates into this window strongly while the radiation issuppressed in the other spectral regions, the heat exchange between thematerial and the atmosphere would be minimized so that the cooling isfacilitated. It has long been recognized that the ideal emissivityconsists of 1 within the atmospheric window and 0 otherwise. However,actual experiment has revealed negligible difference in the sampletemperature between a material close to the ideal emissivity and anotherclose to a black body.

For certain embodiments of the present invention, it has been found thatthe cooling power of a mid-IR black body is actually larger than that ofan ideal emissivity material. Therefore, for maximum cooling, thematerial should exhibit high emissivity in the broad mid-IR range andlow absorptivity in the solar spectrum.

For high emissivity in the mid-IR, many polar materials may be used suchas SiO₂, SiO, SiC, TiO₂, HfO₂, Al₂O₃, ZnO, etc. These materials exhibitresonances in the mid-IR due to atomic vibrations. The resonances aremanifest as a strong dispersion in the dielectric function. Thisdispersion typically involves not only high absorption peaks but alsohigh reflection. For maximum cooling, the reflection should be minimizedIn certain embodiments, the present invention reduces the reflectionloss due to increase emission using microsphere-based structures. In themid-IR, the photon wavelength (˜10 μm) is much greater than the size ofthe microspheres (˜1 μm). In this case, mid-IR light does not “see” thedetailed structures and responds roughly to an average of the dielectricfunction. Based on the effective medium theory, which finds the averagedielectric function, reflection decreases as the filling fraction of themicrospheres decreases. For example, FIG. 3 compares the calculatedmid-IR emissivity spectrum of a solid SiO₂ film and a film of SiO₂microspheres of 55% filling fraction. The calculation is based onMaxwell-Garnett effective medium theory and the films are thick (100μm). The SiO₂ microspheres show high emissivity in the mid-IR and theemissivity is enhanced compared to a solid SiO₂ film. Therefore, thecooling power can be enhanced by decreasing the microsphere fillingfraction in the structures for thick films.

In certain embodiments, the present invention concerns radiative coolercoatings adapted for use with sunlight which consist of multilayerstacks with photonic band gaps to reduce sunlight absorption. In otherembodiments, fabrication of the structures involves layer-by-layerdeposition processes with a precise control of the thickness of eachlayer. Moreover, for efficient suppression of the broad solarabsorption, a large number of layers with several differentperiodicities are required in the multilayer stack. For example, aprevious study used 30 layers to achieve a 3.5% solar absorptivity. Whenmany layers are used, the fabrication cost and time would not be withinthe practical bounds. The embodiments of the present invention overcomethis known problem and achieve similar or even better coolingperformance using random arrangements of microspheres. The coatings ofthe present invention allow for inexpensive manufacturing withoutrequiring precision control. The microsphere-based coatings of thepresent invention can scatter incident light back to the atmosphere sothat solar absorption is reduced. Even when the coating needs to bethick, the thickness does not matter much in terms of the manufacturingand material cost.

The radiative cooling is expected to be most effective in regions of dryatmosphere such as the State of New Mexico (NM). This is because themoisture in the atmosphere is a strong absorber of certain bands in themid-IR. In particular, the atmospheric transparent window 8≤λ≤13 μm issignificantly affected by the water vapor absorption. Thus, as theatmosphere becomes more humid, the atmospheric radiation becomes closerto the black body radiation and the radiative cooling effect decreases.Because of the low relative humidity in NM, the radiative coolingtechnology of the microsphere-based coatings of certain embodiments ofthe present invention would be greatly beneficial. Moreover, theeffective sunlight scattering of the coatings would prevent solarheating in regions of strong sunshine. For example, in the city ofAlbuquerque in N. Mex., average 278 days per year are sunny or partlysunny days.

Light trapping is important in various optoelectronic applications. Forexample, for solar photovoltaics, light trapping inside photoactivelayers enhances energy conversion efficiency. It has also beendemonstrated that photonic nanostructures that are highly efficient inlight trapping in silicon solar cells. The structures diffract lightinto the underneath film and light is trapped in the film throughresonances. An alternative strategy for light trapping is to randomlycorrugate the film surface. For the present invention, when the film ismuch thicker than the light wavelength, the light trapping reaches thethermodynamic limit known as the Lambertian limit. The Lambertian lighttrapping is approximately realized in silicon solar cells by randomlycorrugating the silicon surface. While this strategy is already used incommercial silicon cells, its usefulness in thin-film photovoltaics ishighly questioned because a significant part of the expensivephotoactive layer is lost by texturing. In contrast, additive techniquescan also be used. For example, random metallic particles can be added onthin solar cells for light trapping. However, the plasmonic resonancesin the particles involve significant optical loss. Thus, this techniqueis not commonly used for high efficiency solar cells such as GaAs orCIGS based cells. In certain embodiments of the present invention, adifferent approach that relies on random packing of microspheres torealize the Lambertian light trapping is used.

The microsphere-based coatings of the present invention controlrandomness to minimize reflection loss, while randomizing the lightpath. The degree of randomness is an important parameter that determinesthe level of light trapping. When the coating scatters light toostrongly, a significant fraction of the incident light will beback-scattered as optical loss. If the scattering is too weak, the lightpath randomization will be difficult. Thus, embodiments of the presentinvention adjust the randomness in the microsphere-based coating torealize the Lambertian light trapping with minimal reflection loss.

It has long been noted that the efficiency of solar cells deterioratesas they are heated under sunlight. The typical temperature differencebetween a solar cell and the atmosphere is 50-60° C. at the solarirradiance of 1000 W/m². For silicon solar cells that exhibit 25%efficiency at 25° C., the efficiency drops to ˜21% when the celltemperature reaches 55° C. The heating problem in solar cells becomeseven more serious when they operate with sunlight concentration. Toprevent heating of solar cells, various heat removal systems based onconvection and conduction have been considered. More recently, it wasdemonstrated that radiative cooling will also be effective in increasingsolar cell efficiency. For radiative cooling, a promising experimentalstudy used periodic SiO₂ structures on silicon cells. These structuresreduced the temperature of a silicon solar cell by 13° C. However, thelight trapping effect of the structures was only slight. Moreover, thestructures raise practical fabrication issues. For example, thedeposition of 500-μm-thick SiO₂ films (the study used a SiO₂ plate andan index matching liquid, which would still not be very practical) andthe reactive ion etching of a 10-μm-depth on the film would be timeconsuming and expensive. In comparison, the microsphere-based coatingsof the present invention enable much simpler processing. Further, themid-IR emissivity of the coatings is very high as shown in FIG. 3.Certain embodiments of the present invention have achieved 94.3%emissivity averaged over the mid-IR emission spectrum and angle.Therefore, the microsphere-based coatings of certain embodiments of thepresent invention are very effective in removing heat in solar cells andefficient light trapping is realized with the coatings withoutdecreasing the high mid-IR emissivity.

Langmuir-Blodgett (LB) technique is commonly used to self-assemblemonolayers on a substrate. In this technique, a monolayer of hexagonallyclose-packed structures is formed on a liquid surface is thentransferred onto a substrate that is vertically pulled out of theliquid. By repeating the process, multilayer sphere arrays may befabricated. In this case, the degree of randomness typically increasesas each layer is added. Thus, structures with graded randomness can befabricated. Moreover, the degree of disorder in each layer can becontrolled.

In one preferred embodiment of the present invention, the degree ofrandomness will be controlled in each layer in the LB assembly. Thedisorder may be characterized by image analysis after adding each layer.Light scattering may be characterized by measuring transmission andreflection for SiO₂ and TiO₂ microspheres.

The assembled SiO₂ sphere monolayers made in accordance with anembodiment of the present invention were characterized by laserdiffraction. The average crystalline domain size, G, was obtained fromthe laser diffraction pattern. FIG. 4 shows scanning electron micrograph(SEM) images of the SiO₂ sphere monolayers with the G values in micronsfor various combinations of the pulling speed and the surface pressure.The results show that the structural order can be controlled by thelatter parameters in the LB process. Moreover, the results agree withmodel predictions very well. The comparison between the two is given inFIG. 5 where black dots are experimental points at the largestcrystalline domain size and the lines are model predictions. At moderatepulling speeds, the required surface pressure increases for the secondlayer (b) compared to the first layer (a).

In other embodiments, the present invention may vary the pulling speedand surface pressure in each layer in the LB process to control thedegree of randomness. The randomness of a layer depends not only on thetwo parameters but also on the randomness of the previous layer. Samplepreparations may be categorized as follows: (1) the two parameters areset to the maximum G condition throughout the multilayers, (2) theparameters are gradually detuned from the condition as the layers areadded, and (3) the parameters are initially detuned and are closer tothe maximum G condition as the layers are added. Following thesemethods, the variation of the randomness in the film thickness directionmay be controlled.

Sedimentation of colloidal microspheres is known to induce f.c.c.crystals of a long range order with a (111) plane at the film surface.The sedimentation process may be accelerated using a centrifuge withoutaffecting the order. In the sedimentation process, it is difficult tointroduce a controlled degree of randomness into the crystals. However,it is possible to create almost completely random arrangement ofmicrospheres by inducing colloidal instability. Colloidal microspheresin suspensions are often charged and the interaction between the spheresbecomes repulsive. When the repulsive force dominates the van der Waalsattraction force, the colloid is stable. However, when an electrolyte isadded to the solution, the repulsive potential barrier is lowered. As aresult, the microspheres coagulate when the electrolyte concentrationexceeds a limit known as the critical coagulation concentration. Thiscoagulation process leads to random structures. Thus, layers havingstructures of alternating tiers of order and disorder may be createdusing the sedimentation process above and below the critical coagulationconcentration alternately. A previous study on template directedcolloidal self-assembly showed that, when sphere layers are grown on astructure with a lattice plane different than (111), the structuretransitions into the (111) plane through the gradual introduction ofdefects. Based on this, the sedimentation of stable colloids on randomstructures may result in ordered layers after addition of some number oflayers. In this case, an ordered tier may be deposited on a disorderedtier using the sedimentation method. Therefore, the present inventionadvantageously uses this to obtain structures of alternating ordered anddisordered tiers using the sedimentation process.

Alternating tiers of ordered and disorders structures may be fabricatedusing the sedimentation method of the present invention. The scatteringproperties of the multi-tiered structures based on SiO₂ and TiO₂microspheres may be characterized by transmission and reflectionmeasurement.

KCl salt solution was added to stable SiO₂ microsphere colloids toinduce instability. After the solvent was removed, a film of randomlypacked microspheres was obtained. FIG. 6A shows an SEM image of theresulting structures. The randomness of the structures was characterizedby autocorrelation function as shown in FIG. 6B. The autocorrelationfunction was obtained by analyzing the image contrast in FIG. 6A over anarbitrarily selected line. The function shows the clear signature of therandom structures. Sedimentation without inducing colloidal instabilityresults in well-ordered structures.

In other embodiments, the present invention provides multi-tieredstructures of alternating order and disorder using a sedimentationmethod. For these embodiments of the present invention, the depositionof an ordered film on disordered structures is provided. This may beaccomplished by using sediment stable colloids on random structures withdifferent film thicknesses and sedimentation conditions. Ordered SiO₂ orTiO₂ sphere films may be grown on randomly packed polystyrene spheres.Subsequent selective removal of the polystyrene spheres will result in afilm of the ordered SiO₂ or TiO₂ spheres. The scattering properties ofthe ordered SiO₂ or TiO₂ film can be measured to extract the diffusionparameters. The diffusion parameters of the disordered structures can bedetermined separately with similar measurement on uniform disorderedfilms. The diffusion problem described above may be solved formulti-tiers of alternating order and disorder using the obtainedscattering parameters.

Light propagation in well-ordered tiers depends on the photonic bandstructure. Thus, the actual interaction between the ordered and thedisordered tiers will be more complicated than the prediction by thediffusion equation that ignores the spectral dependence of scatteringparameters. However, for low index microspheres, the modification ofphotonic band structure by the structure periodicity will be weak. Inthis case, the diffusion approximation may be plausible.

In a preferred embodiment, as shown in FIGS. 7A-7E, the microspheresuspension can be directly spray-coated onto a substrate with anairbrush pistol to achieve random structures. FIG. 7A shows an apparatusconsisting of a gravity-fed airbrush 100 (Badger gravity feed series,Model 100G), an air compressor 102 (Badger, TC910 Aspire Pro), and acustom-built, linear-motion, heated stage 104. Spray deposition can beperformed multiple times over the substrate as the stage moves back andforth on a metal platform 106 over heater 108, and the heating dries thefine droplets on the surface in a controlled fashion. The stagetemperature and speed of motor 110 are controlled up to 150° C. and 3.6mm/s, respectively.

The spray process involves a number of parameters such as stage/scanspeed, distance of airbrush from the substrate, flow rate, nozzle outletpressure, and substrate temperature. Substrate temperature is importantfor the drying dynamics of droplets, in which higher substratetemperatures allow for faster drying of the droplets and preventcoalescence into larger droplet before drying. Stage operatingtemperatures may be in the range of ˜130° C. This temperature is highenough to allow for fast evaporation.

Nozzle outlet pressure and distance from the substrate are otherparameters in the deposition process. Increasing pressure results inincreasing pressure drop across the nozzle and subsequently increasingfluid velocity through the airbrush. With increasing pressure, liquiddispersion breaks into smaller/finer ligaments and droplets. Whilenozzle pressure affects the mass flow rate of microsphere suspension,the nozzle distance controls the surface coverage of microspheresdeposited onto the substrate. It was determined for a preferredembodiment of the present invention that the nozzle pressure anddistance of 20 psi and 10 cm, respectively, allow for fast dropletdrying and relatively uniform coats of microspheres after a few stagecycles. See FIGS. 7D-E.

Light scattering in random structures and photonic band gap in periodicstructures may have relations to each other. For example, as therefractive index of a constituent material increases, in general, thescattering strength increases in random media and the photonic band gapwidens in photonic crystals. For 3D structures, the realization of acomplete photonic band gap has proved challenging but a few structuresexhibit such a band gap. A well-known example of 3D photonic band gapstructures is the woodpile structures of a diamond lattice. Thestructures consist of layers of 1D rod arrays with the rod direction ofa layer rotated by 90° at the next layer. When the periodicity of thestructures is destroyed, a random fibrillar network would result.Interestingly, this random structure is recently found in white beetlescales which exhibit the smallest transport mean free path among knownrandom media of low refractive index. The inverse woodpile structuresexhibit even a larger photonic band gap than the woodpile structures.Interestingly, the inverse structures of random fibrillar network,namely the random networks of nanopores, achieved the highest lightscattering efficiency when first introduced in 1999. While the photonicband gap in the woodpiles or the inverse woodpiles is partly due to thediamond lattice, the strong scattering properties that result when thelattice is disturbed might derive from the network structures. Fibrillarnetworks resulting from the disturbance of diamond-bonding networks caneven exhibit a photonic band gap without the periodicity requirement.While the band gap can be explained by the bonding and antibondingphotonic states, it would also indicate extremely strong lightscattering of fibrillar networks. However, the origin of such lightscattering strength manifested by the small transport mean free paths inthe network structures is still largely unknown.

Toward the understanding of the strong light scattering in fibrillarnetworks, it is important to establish the relationship between thestructure and the optical properties. In particular, the transition ofthe optical properties from periodic to random structures may revealimportant physics that relates between the two. The physics may provideinsight on how to realize optical Anderson localization in 3D structureswith hints from the research in photonic band gap materials. Therealization of the Anderson localization has been quite challenging:only a few reports so far claimed success and these reports are stillinconclusive because of the complications such as optical absorption.The establishment of the structure-property relationship will also beimportant in the realization of extremely thin white films usingfibrillar networks which would enable paper-thin displays, solar heatmanagement in buildings and space vehicles, etc.

In other aspects, the present invention provides a method based onself-assembly of SiO₂ or TiO₂ microspheres to fabricate fibrillarnetwork nanostructures. The method is designed to enable the precisecontrol of the structures. FIG. 8 illustrates the following fabricationprocess: (step a) periodic grooves 200-203 are patterned on a surfacewhich may be a c-Si surface 204, (step b) microspheres may be depositedon the surface inside the grooves as monolayer chains by templatedirected self-assembly, (step c) the sphere chain arrays 210-212 may betransferred onto an organic tape 220, (step d) samples of variousperiodicities may be fabricated and stacked with controlledorientations, and (step e) after burning out the tape, the sphere chainarrays will collapse down and form a disordered network 230 of spherechains forming a multilayer coating. As shown in FIG. 8E, a coatinghaving 3 layers is formed but other numbers of layers may be used aswell. Because the developed method provides precise control onstructures, a relationship between the optical properties and thestructures may be established.

For one particular embodiment, the present invention patterned c-Sisurfaces using interference lithography and deposited spheres on thegrooves using the LB method as shown in FIG. 9. A simpler spin coatingcan also be used. After the sphere chains were prepared on c-Sisurfaces, the tape was burned out.

To obtain l*, l, and R for various combinations of the periodicitydistribution, the sphere filling fraction, and the sphere chainorientation may be used. The sphere filling fraction was fixed usingmonodisperse spheres. The distribution of the in-plane periodicity maybe varied in the thickness direction with isotropy to achieve almostcompletely random scattering. Once the periodicity distribution isdetermined, a structure that consists of a periodic stack and a randomstack was fabricated. FIG. 10A illustrates the structure schematicallywith ordered layers 300-305 and disordered layers 310-315. Thisstructure will be compared to a uniform scattering structure in FIG. 10Cthat consists of the same in-plane layers with a different distributionin the thickness direction. The uniform structure in FIG. 10C representsthe complete mixing of the periodic stack and the random stack. Theintermediate mixing of the two stacks may be realized by a number ofdifferent distributions of the same in-plane layers. An example of theintermediate mixing is shown in FIG. 10B. Assuming that the resultingstructure can be regarded as a uniform diffusive medium, the mean freepaths will be obtained to show how the mean free paths depend on thedistribution of the in-plane periodicities. This will reveal how themean free paths increase as a random structure is “diluted” by mixingwith a periodic structure. Based on the results the “dilution” path thatgives the slowest and the fastest increase of the mean free paths may bedetermined. To use the results as a means to finding extremely strongscattering structures, the original undiluted random structure shown inFIG. 10A may be viewed as a structure that is diluted from unknown more“concentrated” structures. This view is similar to treating the FIG. 10Bstructure as one that is diluted from the FIG. 10A structure. In thiscase, the layers with the average periodicity in the original randomstructure can be identified as a periodic “solvent”.

In yet other embodiments, the present invention concerns ways in whichthe transport mean free path, l*, may be changed or altered as desired.For example, the l* for layers 310-315 in FIG. 10A is smaller than thel* for layers 310-315 in FIG. 10B as a result of adding ordered layersin 312 and 313. In turn, the l* for layers 310-315 in FIG. 10C is evengreater than the l* for layers 310-315 in FIG. 10B as a result of addingeven more ordered layers in 311, 312 and 314.

As is also shown, an ordered layer as shown in FIG. 9 may be used tocreate an ordered layer in a tier such as layer 305 for example. Layer305 in FIG. 10A may be created by exfoliating or otherwise transferringthe layer shown in FIG. 9 to the tier.

The same steps may be used with different sphere filling fractions. Foreach filling fraction, the structures of the least transport mean freepaths may be determined. These will determine the filling fractiondependence of the mean free paths. They will also determine the optimumfilling fraction for the smallest mean free paths for both SiO₂ and TiO₂microspheres.

In other embodiments of the present invention, the anisotropy of theoptimum structures may also be determined to minimize the mean freepaths as suggested by the structures in white beetle scales.

In still further embodiments, the present invention provides scatteringmaterial that can be made to scatter light even more strongly than knowbefore. Conversely, in other embodiments, the present invention showshow to mitigate the scattering strength of a material in a highlycontrolled fashion based on the relation between the order-disordermixing and the scattering properties and the ability to control thescattering properties of materials precisely.

The structures based on microsphere chains can model the actualmorphology of fiber or pore networks that are found to provide extremelystrong scattering. Such morphologies include, but are not limited to,curved sphere chains with non-uniform cross-sections. As illustrated inFIGS. 11A and 11B, when grooves are wider than the sphere size,self-assembly will result in non-straight chains (FIG. 11B) as thespheres are connected by capillary forces.

The kinked chain of FIG. 11B has a higher degree of randomness than thelinear chain shown in FIG. 11A. As a result, where desired, kinkedchains may be used or introduced to lower the transport mean free path,l*.

Moreover, using microspheres with polydispersity, randomly non-uniformcross-sections in the fibrils was realized for certain embodiments ofthe present invention. These concepts may also be applied to thelinear-chain structures that are found to exhibit very small transportmean free paths.

In one embodiment of the present invention, the primary materials forthe microspheres may be SiO₂ and TiO₂, which have refractive indices of1.45 and 2.5 (anatase), respectively. However, the dependence of therefractive index on the scattering properties will not be limited tothese two indices. Once the solid structures are fabricated, thestructures may be infiltrated with a liquid with a known refractiveindex to control the refractive index contrast. The refractive index ofthe liquid may be controlled by mixing low and high index liquids invaried ratios. Without liquid infiltration, it is possible that thestructures made of TiO₂ microspheres exhibit Anderson localizationbecause of the high refractive index.

In radiative cooling under sunlight applications, scattering isgenerally desired to reduce sunlight absorption by the materialunderlying the scattering coating. For cooling, it is important toachieve high emissivity in the mid-IR. The high emissivity is notaffected much by the structures because the sphere size is much smallerthan the wavelength of mid-IR radiation. Rather, the emissivity will bedetermined mostly by the sphere filling fraction and the spherematerials. In principle, the sphere filling fraction can be controlledby various methods such as the one that fabricates fibrillar networksdescribed above. However, in real applications, manufacturability of thestructures should be considered. In this respect, the fabricationmethods based on colloidal instability or spray coating would be moresuitable. Because the sphere filling fraction of the structures obtainedby these methods would have a quite limited range, the emissivitycontrol will not be easy in real applications. In fact, the embodimentsof the present invention have achieved a very high emissivity.

In one embodiment, the present invention deposits uniform randomstructures of microspheres on materials mostly using the techniques ofcolloidal instability and spray coating. The solar absorptivity andmid-IR emissivity of the samples may be measured at various randomstructure coating thicknesses, sphere materials, and coating conditions.

Solving the diffusion problem described above, the solar absorptivityfor random SiO₂ microspheres on absorbing materials was calculated. Forinitial estimation, an expected transport mean free path of l*=3 μm andfilling fraction of 55% was used. For the front surface, the properinternal reflectance was taken into account. For the internalreflectance at the interface between the microsphere coating and theabsorbing material, R_(s), two extreme values of 0 and 0.96, whichrepresent an ideal black body and a good metal, respectively wereselected. The actual internal reflectance for a good metal would notreach as high as 0.96 because of the excitation of surface plasmonpolaritons. The calculated solar absorptivity as a function of thecoating thickness is shown in FIG. 12. In general, absorptivitydecreases as the coating thickness increases because of the lightscattering in the coating. The effect of the interface reflectance onthe absorptivity diminishes as the coating becomes thicker. FIG. 12shows that absorptivity for a sphere-coated black body is only 3.4% whenthe coating thickness is 200 μm. With TiO₂ microspheres, theabsorptivity would be even less because of the stronger scattering.

In yet another embodiment of the present invention, uniform random SiO₂spheres of a diameter 900 nm were coated on a Ag film using the methodof colloidal instability and measured absorptivity using an integratingsphere. Absorptivity increases as the wavelength increases. The spectraldependence of absorptivity suggests that the addition of more layers oflarger spheres may be more efficient in reducing absorptivity in thenear-IR. The measured absorptivity (˜0.15) is larger than the value(˜0.05) calculated with R_(s)=0.96 partly due to the excitation ofsurface plasmon polaritons. However, it was found that the measurementhad an error of ˜0.1 in reflectance and transmittance. A recent studyreported a similar level of error for the similar measurement system.While the error was attributed to the light lost in the sample holder inthe past study, the analysis indicates that the scattered light was notcompletely collected by the integrating sphere.

The mid-IR emissivity of a SiO₂ spheres on a Ag film may be measured.The measurement gives an average emissivity with the room temperatureblack body radiation spectrum as a weighting function. The emissivity isalso averaged over the hemispherical solid angle. The measurement gavean emissivity of 0.943 which is already very high

Based on the measured emissivity (0.943) and the predicted absorptivity(0.034), the cooling power in Eq. (5) for a random SiO₂ sphere coatingon a black body (black over the solar spectrum) was calculated. The useof the constant mid-IR emissivity may introduce errors in the coolingpower and the spectral measurement of emissivity will correct theerrors. For the convection and conduction term, the heat transferrelation P_(other)=κ(T_(amb)−T) was used where κ=2.5 W/(m²K) is themeasured value for a device in a past study. The predicted cooling powerwhen the coating thickness is 200 μm and the ambient temperature is 27°C. is given as the middle line in FIG. 13. The cooling power of thecoating is slightly below a mid-IR black body and significantly higherthan an ideal emissivity discussed above. While the cooling powerdecreases most slowly in the case of the ideal emissivity as temperaturedecreases, its magnitude is less than a mid-IR black body. The lowercooling power of the ideal emissivity is due to the fact that the lowmid-IR emissivity of the atmosphere is not limited to 8≤λ≤13 μm as seenin FIG. 2. At steady state, the temperature of the material will reach apoint where the cooling power becomes zero. FIG. 14 shows that, underdirect sunlight, the material with the coating will reach thetemperature of −10° C., which is 37° C. below the ambient temperature.When the material is not a black body (black over the solar spectrum),its temperature will be even lower than −10° C. When the emissivityspectrum predicted from effective medium theory as in FIG. 3 is usedinstead of a constant 0.943, the predicted material temperature is −9.4°C. which is very close to −10° C. For simple processing, the colloidalinstability method and spray coating to deposit the sphere layer wasused. The coating may be a uniform random structure.

As in the previous section, the mid-IR emissivity of the solar cellcoatings are mostly determined by the sphere materials and the spherefilling fraction. When absorption is too small, the efficiency will below. In the opposite case, however, it is not clear if the maximumabsorption will achieve the highest efficiency because of the increasein the cell temperature. The temperature dependence and the absorptiondependence of the photovoltaic efficiency will be different fordifferent cells. To maximize absorption, the microspheres willradiatively cool the cells, which is always an advantage while theoptimum absorption is not clear. To determine the desired distributionof randomness in the tiered coatings for efficient light trapping, thediffusion equation may be used by a microsphere-based coating of auniform randomness on a semi-infinite Si substrate with a perfectantireflection coating. The diffusion problem was solved for thisstructure to obtain absorptivity as a function of the coating thickness.The results are displayed in FIG. 14 for (a) l*=3 μm and (b) l*=200 μm.Here, absorption by diffuse light is shown by the lower line and totalabsorption is shown by the upper line. In both cases, total absorptiondecreases as the coating becomes thicker and the diffuse absorptionexhibits a maximum. When the coating is thick enough, absorption ismostly due to diffuse light. For thin Si films, diffuse absorptionshould be maximized for efficient light trapping. FIG. 14 shows that themaximum diffuse absorption is only 0.67 for the strong scattering (a)but is as large as 0.94 for the weak scattering (b). The requiredcoating thickness for the two cases is 2.2 μm and 5.2 μm, respectively.The results indicate that, for efficient light trapping, weak-scatteringthick structures are desired rather than strong-scattering thinstructures.

For a flat Si surface, the diffuse light is not completely randomizedinside the Si layer. Instead, due to Snell's law, the direction of thediffuse light inside Si is confined within a cone defined by θ=sin³¹¹(1/n) where θ is the angle from the surface normal and n is the indexcontrast between Si and the coating. Thus, for efficient light trapping,the effective index of the coating should be high. However, typicalnon-absorbing materials for microspheres exhibit a refractive indexlower than Si and θ is less than 90°. For the Lambertian light trapping,the Si surface should be corrugated. Because the coating generatesdiffuse light, the corrugation does not have to be deep. When thecorrugation is only shallow, the loss of expensive photoactive layer bycorrugation will be minimal. Therefore, efficient light trapping insemiconductor-based solar cells requires weak-scattering thick coatingson slightly corrugated surfaces with an antireflection coating.

The example of l*=200 μm in FIG. 14B represents highly orderedstructures. The desired structures of tiered randomness will maximizediffusive intensity at the semiconductor interface while minimizingreflection loss. Semiconductor surfaces may be slightly corrugate tomaximize light trapping. For the corrugation, periodic structures withcontrolled depths of corrugation may be used. In other embodiments, thesurface of working solar cells will be corrugated, an antireflectioncoating will be applied on the surface, and the microspheres will becoated on top.

In yet other embodiments, coatings are provided that effectively andefficiently scatter sunlight. The scattering strength may becharacterized by the so-called transport mean free paths (l*). Thetransport mean free path is the length over which light loses its memoryof original direction while traveling in a scattering medium.Approximately, solar absorption is linearly proportional to l* in thickcoatings. l* depends on both the particle diameter d and the fillingfraction f. For randomly packed single size spheres, f ranges between0.55 and 0.64. A powerful method to determine l* is coherent potentialapproximation (CPA), which is known to be highly accurate for any f. Thecalculated l* for the two extreme values off in randomly packed SiO₂spheres of 0.9 μm in diameter d is compared in FIG. 15. The resultsshould be between the two predicted values and is closer to theprediction for f=0.64. The CPA predictions of t agree remarkably wellreproducing even the detailed spectral features. Because l* increases asthe light wavelength λ increases in this case, absorption will alsoexhibit the same trend when the microsphere-based coating is placed onan absorbing material. For example, when a microsphere coating of athickness L=700 μm is on a black body, absorption A≈2l*/L is expected tobe 0.7% and 11% at λ=0.4 μm and 2.5 μm, respectively. Therefore, withthe d=0.9 μm microspheres, solar absorption in the near IR issignificant and this increases the temperature of a material underneaththe coating. Commercial paints also suffer from IR absorption bymaterials underneath the paints in even higher degrees.

The near IR absorption can be reduced by using different size spheres.FIG. 16 shows calculated l* in the solar spectrum at various spherediameters. It is revealed that l*, hence solar absorption, is minimizedwhen the sphere size is d=4 μm. In general, l* decreases as d increasesup to 4 μm with the effect being most pronounced in the longwavelengths. When d is larger than 4 μm, l* increases as d increasesprimarily in the short wavelengths. When d is much larger than λ, l* canbe estimated based on the theory developed by Kubelka-Munk andBrewster-Tien. The estimation gives

$l^{*} \cong {\frac{d}{3\; f}.}$

Thus, l* is linearly proportional to d for large spheres.

For example, when d=50 μm, l* is estimated to be 30.3 μm. Popular lowrefractive index pigments used in commercial solar reflective paints areof a shape of hollow spherical shells of d=20-150 μm. Therefore, thesphere size of popular commercial paints based on low refractive indexpigments leads to much weaker light scattering than the coatings of thepresent invention.

Brewster-Tien criterion says that, when spheres are large enough, thefilling fraction of spheres does not significantly affect the scatteringefficiency of each particle. However, for small size spheres, it hasbeen reported that light scattering strength is maximized at a spherevolume fraction of roughly around f=0.2.⁸ Because the filling fractionin random packing is larger than this value, the dependence of l* on ffor random packing was analyzed. FIG. 17 shows this dependence atselected wavelengths in the solar spectrum when the diameter of SiO₂spheres is 4 μm. The region of f>0.64 corresponds to the case wheremicrospheres are sintered. Overall, l* increases as f increases, whilean opposite behavior is observed at short wavelengths. The spectralaverage of l* is minimum at f=0.55. Thus, for maximum scattering ofsunlight, it is desired to minimize the sphere volume fraction in randompacking.

The cooling effect of white coatings can be characterized by l* averagedwith a solar spectrum as a weighting factor. This average <l*> isapproximately proportional to the solar power absorbed by the materialunderneath a coating, P_(sun), because

${P_{sun} = {{{\int{{A(\lambda)}{I(\lambda)}d\; \lambda}} \cong {\int{\frac{2\; {l^{*}(\lambda)}}{L}{I(\lambda)}d\; \lambda}}} = {\frac{2}{L}{\langle l^{*}\rangle}{\int{{I(\lambda)}d\; \lambda}}}}},$

where l(λ) is the sunlight spectrum and <l*> is defined by

${\langle l^{*}\rangle} \equiv \frac{\int{{l^{*}(\lambda)}{I(\lambda)}d\; \lambda}}{\int{{I(\lambda)}d\; \lambda}}$

FIG. 18 shows 1/<l*>, which is a measure of sunblock performance, as afunction of d and f for SiO₂ microspheres. The maximum sunblockperformance is obtained when d=4 μm and f=0.55. The optimum fcorresponds to the minimum achievable value for random sphere packing.It is known that, as the sphere size distribution becomes wider, thesphere fraction decreases. This is schematically illustrated in FIG. 19.In FIG. 19, the sphere filling fraction is low when monodisperse spheresare randomly packed (left) and is high when polydisperse spheres arepacked (right). Thus, it is desired that the spheres are monodisperse tomaximize the sunblock power of the coatings. Current commercial paintsbased on pigments of a low refractive index consist of highlypolydisperse particles ranging from 20 to 150 μm in size. At these largesizes, polydispersity is desirable for light scattering because, basedon the relation

${l^{*} \cong \frac{d}{3\; f}},$

increase in f results in decrease in l*. However, for sphere sizes nearthe optimum for sunblock, monodisperse spheres are desired.

TiO₂-based paints exhibit optical characteristics that are differentfrom SiO₂ microspheres because of the high refractive index of thepigments. Paints based on rutile TiO₂ particles typically includebinders and fillers. The refractive indices of the medium materials andthe rutile TiO₂ particles are approximately 1.5 and 2.8, respectively.Commercial solar reflective TiO₂ paints use particles of 200-250 nm insize to maximize scattering in the visible wavelengths. However, solarspectrum includes more than a half of the power in the near IR spectrumλ>700 nm and the TiO₂ particles of the size range are not efficient inblocking IR sunlight.

FIG. 20 shows the dependence of 1/<l*> on the TiO₂ sphere diameter andfilling fraction. The refractive indices of the medium material and theTiO₂ particles are set to 1.54 and 2.74, respectively. Sunblockperformance is maximized when the particle diameter is 1 μm and thefilling fraction is 26%. Current commercial paints with a TiO₂ particlediameter of 200-250 nm show much smaller sunblock performance for allfilling fractions between 0.2 and 0.6. To verify the results, thetemperature of a silicon wafer when coated with a commercial TiO₂-basedpaint was measured. Electron micrographs of the paint confirmed that theparticle size is 200-250 nm. For comparison, a silicon wafer is coatedwith randomly packed SiO₂ spheres of d=0.9 μm. The two samples had asimilar coating thickness and were exposed to direct sunlight. Tominimize convective heat transfer, the samples were housed in a box madeof a transparent film. The sample with a commercial TiO₂-based paint was8° C. higher than the one coated with SiO₂ spheres. Calculated l* was 45μm and 19 μm for the TiO₂ commercial paint and the SiO₂ sphere packing,respectively. Therefore, the calculation is consistent and when a paintwith TiO₂ particles of d=1 μm is used, l* is only ˜2 μm which is morethan 20 times smaller than that of the commercial paint.

In yet other embodiments, for efficient light scattering, the presentinvention uses hollow microspheres that consist of nanoshells. Thesehollow microspheres are directly mixed with binders that are typicallyused for paints. In a preferred embodiment, the binders are polymericmaterials. The contrast in refractive index between the binder and theair inside the hollow microspheres is used for efficient lightscattering. In this case, the size range of the hollow microspheres is1-3 microns and the nanoshell thickness is on the order of 1-10 nm.

In yet other embodiments, rather than have the coatings described abovebeing cooled by radiating thermal energy in the mid-IR spectrum, thepresent invention may be comprised of a substrate that may be in theform of a sheet that is transparent in the mid-IR spectrum andefficiently scatters sunlight. In this embodiment, the object under thesheet is cooled under sunlight, rather than the substrate itself. Thesubstrate functions both as a sunlight blocker and a mid-IR window forthe object. In operation, the object will lose heat by thermal radiationthat passes through the substrate into the space in the universe, whilenot being heated by sunlight. The substrate of this embodiment may bemade of polyethylene that is transparent to the mid-IR spectrum.

In yet other embodiments, the fabrication of a polyethylene substratecan be accomplished by the use of fiber spinning, the deposition ofpolyethylene microspheres, or the formation of microbubbles within apolyethylene sheet/substrate. In yet other embodiments, the presentinvention may co-deposit polyethylene with other materials that aresubsequently etched away. For example, polyethylene and another polymeris co-deposited by using fiber spinning and the polymer is selectivelyetched. Similarly, polyethylene microspheres are mixed with themicrospheres of other materials. After the microsphere mixture isdeposited by spraying or colloidal methods, the microspheres of othermaterials are selectively etched. For microbubble formation, similartechniques can be used.

In still further embodiments, thermochromic pigments may be used in themicrosphere coatings of the present invention. These coatings areconfigured to become dark when the atmosphere is cold and bright whenwarm. For these embodiments, the coating will cool down in summer andwarm-up in winter.

While the foregoing written description enables one of ordinary skill tomake and use what is considered presently to be the best mode thereof,those of ordinary skill will understand and appreciate the existence ofvariations, combinations, and equivalents of the specific embodiment,method, and examples herein. The disclosure should therefore not belimited by the above described embodiments, methods, and examples, butby all embodiments and methods within the scope and spirit of thedisclosure.

1. A surface coating for cooling a surface by light scatteringcomprising: a plurality of successive layers; each of said layerscomprised of a plurality of spheres arranged to form a structurecomprised of packed or non-packed spheres; and each structure of eachlayer has a different arrangement of packed or non-packed spheres tocreate to a different light scattering property in each of said layers.2. The coating of claim 1 wherein said structures are formed by randomlypacked spheres and said spheres have a uniform diameter.
 3. The coatingof claim 2 wherein said coating emits light in a range of 8-13 microns.4. The coating of claim 3 wherein said coating also emits light in arange of 18-30 microns.
 5. The coating of claim 1 wherein each of saidlayers has a fixed periodicity and the periodicity of each layer isdifferent.
 6. The coating of claim 1 further including multilayers ofspheres with a predetermined degree of randomness.
 7. The coating ofclaim 1 wherein said layers are comprised of lateral periodic structuresand non-periodic structures.
 8. The coating of claim 7 wherein saidperiodic layers are ordered structures and said non-periodic structuresare random structures.
 9. The coating of claim 1 wherein each of saidlayers are made of a monolayer of microspheres with a predetermineddegree of randomness.
 10. The coating of claim 1 wherein each of saidlayers have a sphere filling fraction of less than 55%.
 11. The coatingof claim 1 wherein each of said layers have a sphere filling fractionbetween 20-45% and said spheres have a diameter between 0.4 and 1micron.
 12. The coating of claim 5 wherein each of said layers hasspheres joined into fibrillar networks and said fibrillar networks ofeach layer have different periodicities and orientations.
 13. A methodfor cooling a substrate by applying a coating to the surface of thesubstrate comprising the steps of applying layers of spheres by randomlypacking said spheres on said surface wherein the cooling power isenhanced by decreasing the sphere filling fraction to a filling fractionof less than 55% in each of said layers.
 14. The method of claim 13wherein said spheres have a uniform diameter between 0.8 and 3 microns.15. The method of claim 13 wherein said layers are comprised of tiers ofrandomly distributed spheres and the degree of randomness of each tierincreases or varies with each successive layer.
 16. The method of claim13 wherein said layers are made using the sedimentation of colloidalspheres, and said spheres and said substrate are adapted to haveattractive charges to create random layers of microspheres.
 17. Themethod of claim 16 wherein said random layers are made by inducingcolloidal instability. 18-34. (canceled)